WO2006085541A1 - Procede de production d’un gel et d’une solution hautement visqueuse de tanin - Google Patents

Procede de production d’un gel et d’une solution hautement visqueuse de tanin Download PDF

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Publication number
WO2006085541A1
WO2006085541A1 PCT/JP2006/302133 JP2006302133W WO2006085541A1 WO 2006085541 A1 WO2006085541 A1 WO 2006085541A1 JP 2006302133 W JP2006302133 W JP 2006302133W WO 2006085541 A1 WO2006085541 A1 WO 2006085541A1
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WO
WIPO (PCT)
Prior art keywords
tannin
gel
concentration
salt
solution
Prior art date
Application number
PCT/JP2006/302133
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English (en)
Japanese (ja)
Inventor
Tomoaki Matsuo
Original Assignee
Kagoshima University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kagoshima University filed Critical Kagoshima University
Priority to JP2007502617A priority Critical patent/JP4677567B2/ja
Publication of WO2006085541A1 publication Critical patent/WO2006085541A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0056—Preparation of gels containing inorganic material and water

Definitions

  • the present invention relates to a method for producing a tannin gel and a highly viscous solution.
  • Tannins are natural products that are extracted from plant trunks, skins, leaves, fruits, etc., and are environmentally friendly substances that are generally used as skin tanning agents. Tannins include pyrogallol-based hydrolyzable tannins and catechol-based condensed tannins. With the help of hydrolyzed tannin, which is a relatively small molecule, many plant materials such as herbal medicines have been isolated and identified, and basic research has been done using only this type of tannin. . On the other hand, condensed tannin was not clearly identified. In 1989 Weinges named proanthocyanidin a substance that produces anthocyanin when a colorless plant extract is heated with acid.
  • a substance consisting of a plurality of linked flavonoid units with a component strength of 3 ⁇ 4avan-3-ols was defined as open anthocyanin.
  • condensed tannins it has been clarified that many fruit components are proanthocyanidin polymers, and many studies on condensed tannins (proanthocyanin polymers) have been conducted.
  • the plant that is the raw material of the tannin can be supplied by afforestation or the like, and the afforestation site is said to be a 10-year cycle in the case of a black wattle in South Africa, for example. Therefore, the tannin can be supplied continuously without burdening the global environment like logging of southern ocean timber, and consideration is given to resource depletion such as synthetic resin produced from petroleum products. There is no need.
  • tannin is an aqueous solution of an aqueous solution of tannin, a natural resin extracted from wood, as an alternative to formaldehyde-based adhesives that have problems such as sick house syndrome and chemical sensitivity. It is known to be used as an adhesive (see Non-Patent Document 1, for example).
  • Non-patent document 1 Yoshikazu Yazaki, "Natural products for wood (tannin) -based adhesives", Journal of the Adhesion Society of Japan, 2001, No. 37, No. 12, pp. 25-30
  • An object of the present invention is to impart new physical properties to tannin and to effectively use tannin.
  • the present invention includes the following inventions.
  • a tannin aqueous solution at least one selected from boric acid, phosphoric acid and water-soluble salts thereof as a first gelling agent is added and mixed, and then an alkali as a second gelling agent.
  • a method for producing a gel or highly viscous solution comprising adding a metal salt or an alkaline earth metal salt and stirring.
  • alkali metal or alkaline earth metal halide is at least one selected from potassium chloride, calcium chloride, and magnesium chloride.
  • a tannin gel and a highly viscous solution are provided, which can be used in various applications.
  • Tannin is a natural product extracted from plant trunks, skins, leaves, fruits, etc., and is an environmentally friendly material. Tannin includes pyrogallol-based hydrolyzable tannin and catechol-based condensed tannin.
  • the tannin used in the present invention is not particularly limited.
  • tropical 'subtropical fruits' tannin from which mosquitoes such as apples are extracted, kakitannin from which repulsive force is also extracted ((+)-powered textiles) , (+) -Epicatechin polymers), wattle tannin, quebrachio (kebraco) tannin, radiata pine tannin, gallic tan, pentaploid tan, etc.
  • tannins extracted from eucalyptus, mangroves and Japanese larch The tannin may have increased solubility in water by chemical modification such as sulfone.
  • the tannin is usually dried and used as a powder after extraction from the raw material.
  • the powdered tannin dissolved in water is used as the tannin aqueous solution V.
  • the extract from the raw material may be used as it is as the tannin aqueous solution.
  • the raw materials for tannin (for example, oyster astringent for oyster tannin) contain organic acids, amino acids, etc. in addition to tannin. May be.
  • the tannin concentration in the tannin aqueous solution is usually 0.5 to : LO weight
  • the amount is preferably 1 to 4% by weight, more preferably 1.5 to 3% by weight
  • the pH is usually 4 to 10, preferably 6 to 9.
  • the borate used as the first gelling agent includes, for example, sodium borate, potassium borate, ammonium borate, triethanolamine borate, preferably sodium borate, phosphoric acid.
  • Examples include potassium acid.
  • the concentration of boric acid or its water-soluble salt in the solution is usually 0.5 to 5% by weight, preferably 1 to 3% by weight.
  • an alkali metal salt or alkaline earth metal salt other than the alkali metal salt of boric acid or phosphoric acid is used.
  • examples include metal or alkaline earth metal halides (eg, sodium chloride, potassium salt, calcium salt, magnesium salt), and lactate salts (eg, calcium lactate).
  • the alkali metal salt or alkaline earth metal salt used as the second gelling agent is preferably a water-soluble calcium salt or magnesium salt (for example, calcium chloride, magnesium chloride, calcium lactate).
  • a natural polymer solution such as milk containing a magnesium salt can be used.
  • the concentration of the alkali metal salt or alkaline earth metal salt in the solution is usually 0.05 to 5% by weight, preferably 0.25 to 1% by weight.
  • the weight ratio of boric acid or its water-soluble salt used as the first gelling agent to the alkali metal salt or alkaline earth metal salt used as the second gelling agent is usually 1 to: LO: l, preferably 2-4: 1.
  • tannin gel or a highly viscous solution can be produced as appropriate.
  • a gel of tannin can be produced by adding 0.25 to 4% by weight of an alkali metal salt or alkaline earth metal salt as the gelling agent 2 and stirring.
  • the pH is adjusted beforehand to hydrochloric acid, sulfuric acid, acetic acid, citrate.
  • the tannin concentration is usually 3 to 8% by weight, preferably 4 to 6% by weight.
  • the tannin concentration is adjusted to slightly alkaline, preferably pH 7.2 to: LO. 0, more preferably around pH 9, using a 1M aqueous sodium bicarbonate solution or other buffer.
  • Thereto is added at least one aqueous solution selected from phosphoric acid, which is the first gelling agent, and a water-soluble salt thereof, while gradually stirring.
  • the final concentration is 50 ⁇ : LOOmM is appropriate.
  • the phosphoric acid and its water-soluble salt used here are not particularly limited, but those that are recognized as food additives are preferred when applied to foods and the like.
  • phosphoric acid or “phosphate”
  • phosphoric acid or “phosphate” in a broad sense, that is, polyphosphoric acid such as orthophosphoric acid, pyrophosphoric acid, metapyrophosphoric acid, or These water-soluble salts are shown.
  • Phosphoric acid and its water-soluble salts recognized as food additives include, for example, phosphoric acid (orthophosphoric acid), dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium trihydrogen phosphate, phosphoric acid.
  • examples thereof include disodium hydrogen, sodium dihydrogen phosphate, sodium trihydrogen phosphate, sodium dihydrogen pyrophosphate, tetrapotassium pyrophosphate, and potassium polyphosphate.
  • the alkali metal salt or alkaline earth metal salt preferably calcium salt, magnesium salt, more preferably calcium salt, especially salt calcium salt is terminated.
  • a gel is obtained when the concentration is increased to 50-500 mM.
  • Addition of an acidic polymer compound having an acidic group such as a carboxyl group, such as bectinic acid, polygalacturonic acid, or alginic acid, as a gel-forming auxiliary agent results in a highly viscous solution having a different viscosity or a gel having a different strength. Can be made.
  • the treatment temperature in the present invention is usually 10 to 40 ° C, preferably 15 to 25 ° C.
  • tannin gels or highly viscous solutions can be produced as appropriate.
  • the tangyungel produced in this way is reversibly converted into an aqueous tannin solution by treatment with a chelating agent such as EDTA, EGTA, DTPA, HBED, HDTA, or HEDTA. It can also be made into a solution by an appropriate heat treatment or an organic solvent such as DMF or DMSO.
  • a highly viscous solution of tannin can be produced by reducing the concentration of boric acid, phosphoric acid or their water-soluble salts and alkali metal salts or alkaline earth metal salts.
  • FIG. 1 is a diagram showing a standard curve of catechin.
  • FIG. 2 is a graph showing the relationship between tannin concentration and viscosity of a purified oyster tannin solution.
  • FIG. 3 is a graph showing the relationship between pH and viscosity of a purified oyster tannin solution.
  • FIG. 4 is a graph showing the relationship between the salt concentration and viscosity of a purified oyster tannin solution.
  • FIG. 5 is a graph showing the relationship between tannin concentration and turbidity change. The arrow indicates the point where the gelation occurs.
  • FIG. 6 is a graph showing the relationship between sodium borate concentration and turbidity change. The arrow indicates the point where the gelling occurs.
  • FIG. 7 is a graph showing the relationship between calcium chloride concentration and turbidity change. The arrow indicates the point where the gelling occurs.
  • FIG. 8 is a graph showing the relationship between tannin concentration and gel strength.
  • FIG. 9 is a graph showing the relationship between sodium borate concentration and gel strength.
  • FIG. 10 is a graph showing the relationship between calcium chloride concentration and gel strength.
  • FIG. 11 A graph showing changes in turbidity when calcium chloride, magnesium chloride, and potassium chloride are used.
  • FIG. 12 is a graph showing gel strength when using calcium chloride, magnesium chloride, and potassium chloride.
  • the polyphenol concentration was measured using the Folin—Chioalteu method.
  • a commercially available catechin was dissolved in distilled water to make a catechin solution (g / ml). As shown in Table 1, the catechin concentration was changed, and the absorbance was measured by the Folin-Chiocalteu method.
  • the purified oyster tannin solution was diluted to an appropriate concentration (400, 500, 600 times), the absorbance was measured by the procedure of Folin-Chiocalteu method, and the catechin standard curve force was also determined as the polyphenol concentration (tannin concentration).
  • Tannin solutions with various salt concentrations were prepared.
  • the NaCl concentration was adjusted to 0.5%, 1%, 2%, and 5% and dissolved in the oyster tannin solution.
  • the conditions for gelation were examined using the purified oyster tannin solution obtained in Production Example 1, sodium borate and calcium chloride.
  • Calcium chloride dihydrate was prepared in distilled water with various concentrations.
  • the cachytannin solution and sodium borate were mixed. Add the salty calcium solution and mix well.
  • Table 2 shows the reaction conditions for gelation when the tannin concentration was changed, the sodium borate concentration was changed, and the salt calcium concentration was changed.
  • tannin concentration As shown in Table 2, the gelling speed changes when the conditions are changed.
  • tannin concentration As shown in Table 2, the gelling speed changes when the conditions are changed.
  • tannin concentration As shown in Table 2, tannin concentration
  • One of the measures for measuring the gelation rate is a method for examining turbidity.
  • the gely reaction of kakitannin with sodium borate and calcium salt is accompanied by a change in turbidity. Therefore, the gelation reaction rate was clarified by measuring the change in turbidity.
  • gels there are various types of gels such as soft pudding, pudding, gels, solids like plastic, and gels.
  • the gel strength is one of the properties. Gel strength is a very important part of determining the use of the gel. Therefore, the gel strength of the kakitannin gel prepared with sodium borate and calcium chloride was measured.
  • Kakitannin gel Kerkitannin solution, sodium borate, calcium chloride salt), cutter, grid underlay, fruit hardness tester (Fujiwara Seisakusho KM type)
  • a gel was prepared by the method (1), and the resulting gel was cut into a cube of 1 cm square.
  • the gel strength was measured using a fruit hardness tester (Fujiwara Seisakusho KM type). Vertical, horizontal, and length are all placed on a cube gel cut to 1 cm, and a 1 cm 2 cm thin underlay is placed on the fruit hardness tester. Read memory.
  • Kakitan Yungel made with sodium borate and calcium chloride was expected to be a reversible gel.
  • Kakitannin gel (Kakitannin solution, sodium borate, calcium chloride), EDTA [0088] Method:
  • Kakitan Yungel was prepared. (Tannin concentration 1.6%, sodium borate concentration 2.5%, salty calcium concentration 0.5%)
  • Kakitannin solution sodium borate, magnesium chloride, barium chloride, salted iron (11), potassium chloride, sodium chloride
  • Purified oyster tannin solution obtained in Production Example 1 (tannin concentration 5%) 3 ml of 4M dipotassium hydrogen phosphate aqueous solution 0.1 ml was added and stirred, and then 4M saline-calcium aqueous solution (pH 7.65) was added. When the mixture was mixed with 0.05 to 0.4 ml and stirred, a soft gel was formed in 10 minutes to 1 hour. Optionally, add 1% acidic polymer water solution before adding calcium chloride. 1 to 0.6 ml was added.
  • the gel thus produced could be made into a solution by an appropriate heat treatment, a chelating agent treatment, an organic solvent such as DMF or DMSO.
  • the equipment used was Leonard RE-3305 from Yamaden Co., Ltd.
  • agar powder As a comparative control, commercially available agar (Nakarai Testa Co., Ltd .: agar powder; gel strength 600-700 gZcm 2 ) was dissolved by heating to 0.5%, and a plastic cylindrical container (diameter 14 mm, length 45 mm) The gel was prepared by pouring it into the flask and cooling it. 3. A 75% oyster tannin solution (extracted and purified from astringent oysters) was charged with 10 ml of 1M dipotassium hydrogen phosphate (2.6%). After mixing well, 40 ml of a commercial aqueous formaldehyde solution was added and mixed quickly and poured into a plastic cylindrical container. Measurements were taken after 5 hours.
  • a similar gel could be made by adding 1M calcium salt.
  • the gel was made by quickly pouring into a container (final concentration: about 0.9%).
  • the gel obtained by the method of the present invention is finely crushed and added to the feed.
  • Anti-acidic feed with a high polyphenol content can be given to poultry, livestock and pets, and it can be expected to reduce stress, lower blood pressure and recover from fatigue.
  • the high-viscosity solution obtained by the method of the present invention can be used as a paint on paper or wood, or as a dye on yarn or cloth, and is superior in durability to the case of using a conventional tannin aqueous solution. I can do things. In addition, it is expected to be waterproof, insect-proof, bacteriostatic, abrasion-resistant, deodorant, etc., so it can be used as a coating agent for various containers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Feed For Specific Animals (AREA)
  • Fodder In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Selon l’invention, une utilisation plus efficace d'un tanin est réalisée en lui conférant de nouvelles propriétés physiques. L’invention décrit plus spécifiquement un procédé de production d’un gel ou d’une solution hautement visqueuse qui est caractérisé en ce que au moins une substance choisie parmi des acides boriques, des acides phosphoriques et des sels hydrosolubles de ceux-ci est ajoutée et mélangée dans une solution aqueuse de tanin en tant que premier gélifiant, et ensuite un sel de métal alcalin ou un sel de métal alcalinoterreux est ajouté à cette solution en tant que second gélifiant et le mélange résultant est agité.
PCT/JP2006/302133 2005-02-10 2006-02-08 Procede de production d’un gel et d’une solution hautement visqueuse de tanin WO2006085541A1 (fr)

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JP2007502617A JP4677567B2 (ja) 2005-02-10 2006-02-08 タンニンのゲル及び高粘性溶液の製造方法

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JP2005214235 2005-07-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184285A (ja) * 2011-03-03 2012-09-27 Kagoshima Univ 高分子タンニンの高粘性溶液及びゲルの製造方法
CN107125438A (zh) * 2016-02-29 2017-09-05 湖南晶天科技实业有限公司 一种饲料添加剂鞣酸生物碱及其制备方法以及一种复合添加剂和一种饲料
CN107312120A (zh) * 2017-06-05 2017-11-03 中国林业科学研究院林产化学工业研究所 一种植物单宁水凝胶及其制备方法和应用
JP2019099546A (ja) * 2017-12-07 2019-06-24 株式会社カミノ 消臭・除菌剤

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5881743A (ja) * 1981-11-09 1983-05-17 House Food Ind Co Ltd 紅茶ゼリ−の製造法
JPH08280327A (ja) * 1995-04-14 1996-10-29 Nisshin Flour Milling Co Ltd アミラーゼ阻害物質を含有する茶飲料
JP2000245347A (ja) * 1999-02-26 2000-09-12 House Foods Corp 紅茶抽出物及びこれを含むゲル状食品
JP2000245362A (ja) * 1999-03-03 2000-09-12 House Foods Corp ゼリー食品及びその製造方法
JP2001299297A (ja) * 2000-04-28 2001-10-30 Itoham Foods Inc ゼリー飲料
JP2002306126A (ja) * 2001-04-16 2002-10-22 Sanei Gen Ffi Inc タンニン含有組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5881743A (ja) * 1981-11-09 1983-05-17 House Food Ind Co Ltd 紅茶ゼリ−の製造法
JPH08280327A (ja) * 1995-04-14 1996-10-29 Nisshin Flour Milling Co Ltd アミラーゼ阻害物質を含有する茶飲料
JP2000245347A (ja) * 1999-02-26 2000-09-12 House Foods Corp 紅茶抽出物及びこれを含むゲル状食品
JP2000245362A (ja) * 1999-03-03 2000-09-12 House Foods Corp ゼリー食品及びその製造方法
JP2001299297A (ja) * 2000-04-28 2001-10-30 Itoham Foods Inc ゼリー飲料
JP2002306126A (ja) * 2001-04-16 2002-10-22 Sanei Gen Ffi Inc タンニン含有組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184285A (ja) * 2011-03-03 2012-09-27 Kagoshima Univ 高分子タンニンの高粘性溶液及びゲルの製造方法
CN107125438A (zh) * 2016-02-29 2017-09-05 湖南晶天科技实业有限公司 一种饲料添加剂鞣酸生物碱及其制备方法以及一种复合添加剂和一种饲料
CN107312120A (zh) * 2017-06-05 2017-11-03 中国林业科学研究院林产化学工业研究所 一种植物单宁水凝胶及其制备方法和应用
CN107312120B (zh) * 2017-06-05 2020-02-21 中国林业科学研究院林产化学工业研究所 一种植物单宁水凝胶及其制备方法和应用
JP2019099546A (ja) * 2017-12-07 2019-06-24 株式会社カミノ 消臭・除菌剤

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JPWO2006085541A1 (ja) 2008-06-26

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